EP0017893B1 - Process for the preparation of heterocyclic tertiary aralkyl amines - Google Patents

Process for the preparation of heterocyclic tertiary aralkyl amines Download PDF

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Publication number
EP0017893B1
EP0017893B1 EP80101856A EP80101856A EP0017893B1 EP 0017893 B1 EP0017893 B1 EP 0017893B1 EP 80101856 A EP80101856 A EP 80101856A EP 80101856 A EP80101856 A EP 80101856A EP 0017893 B1 EP0017893 B1 EP 0017893B1
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Prior art keywords
methyl
parts
prop
phenyl
enal
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German (de)
French (fr)
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EP0017893A1 (en
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Norbert Dr. Goetz
Leopold Dr. Hupfer
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BASF SE
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BASF SE
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Priority claimed from DE19792939060 external-priority patent/DE2939060A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D205/00—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D205/02—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D205/04—Heterocyclic compounds containing four-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members

Definitions

  • the present invention relates to a process for the preparation of aralkylamines by reacting aralkenals or aralkanals with secondary amines.
  • tertiary amines can be obtained by reacting secondary amines with carbonyl compounds in the presence of hydrogen and a hydrogenation catalyst (Houben-Weyl "Methods of Organic Chemistry" 4/2, p. 328 ff, 11/1, p. 602 ff, p. 643 ff).
  • German patent 1179947 describes the synthesis of N-alkylated aromatic amines by reductive alkylation of aromatic amines over a palladium-silver catalyst while protecting the aromatic system.
  • the production of tertiary aliphatic or cycloaliphatic amines can also be carried out with a palladium-silver catalyst by reacting aliphatic or cycloaliphatic carbonyl compounds with secondary amines in the presence of hydrogen.
  • a palladium-silver catalyst by reacting aliphatic or cycloaliphatic carbonyl compounds with secondary amines in the presence of hydrogen.
  • Suitable carbonyl compounds include, in particular, saturated ketones, such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone and, in principle, aldehydes which do not undergo any or only difficult adol condensation, such as formaldehyde, isobutyraldehyde, 2-ethylhexanal.
  • German patent application P2 830999 describes the preparation of stereoisomeric N-aralkyl-2,6-dimethylmorpholines by reacting stereoisomeric 2,6-di-dimethylmorpholines with carbonyl compounds in the presence of hydrogen and a palladium-silver catalyst.
  • R 1 is a hydrogen atom, an aliphatic radical having 1 to 10 carbon atoms, a cycloaliphatic radical having 5 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms
  • R 2 , R 3 and R 4 are a hydrogen atom or an alkyl radical having 1 to 4 Carbon atoms
  • X 1 , X 2 , X 4 is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms
  • a the rest and X5, X6, X7, X8, X9 and X 10 represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms and n represents the numbers 1, 2, 3 or 4, by reacting secondary amines of the formula II in which X 1 , X 2 , X 3 , X 4 and A have the meaning given above, with carbonyl compounds of the formula 111 in which R 1 , R 2 , R 3
  • the advantage of the process according to the invention is that in particular sensitive carbonyl compounds, such as ⁇ , ⁇ -unsaturated aldehydes or ketones, which the amines could attach to the double bonds and then could not give rise to uniform end products, or aldehydes or ketones which could undergo aldol condensation, can be used and result in uniform end products.
  • sensitive carbonyl compounds such as ⁇ , ⁇ -unsaturated aldehydes or ketones, which the amines could attach to the double bonds and then could not give rise to uniform end products, or aldehydes or ketones which could undergo aldol condensation, can be used and result in uniform end products.
  • Another advantage of the process according to the invention is that the desired end products of the formula are obtained in a very clean form due to the high selectivity of the catalysts used.
  • the by-products to be expected in this type of reaction such as, for example, the alcohols of the formula to be expected from the carbonyl compounds by hydrogenation or unsaturated amines of the formulas hardly received.
  • the amine component can be used in a stoichiometric amount, based on the carbonyl compound, or in an up to 10-fold molar excess by the process according to the invention.
  • the known starting products III can be prepared by aldol condensation of appropriately substituted benzaldehydes with aliphatic aldehydes or ketones.
  • the hydrogenated compounds are obtained from the unsaturated products by partial hydrogenation of the carbon-carbon double bond (US Pat. No. 2,976,321).
  • the reaction can be carried out both continuously and batchwise, preferably in the liquid phase.
  • the catalyst system used by the process of the invention contains, on the one hand, palladium as the hydrogenation metal and, on the other hand, the additional components zinc, cadium, manganese or an oxide of the rare earth metals or mixtures of oxides of the rare earth metals, it being possible for the additional components mentioned to be present alone or in a mixture with one another in addition to the palladium .
  • These catalyst additives result in an increase in the selectivity of the hydrogenation catalyst.
  • the oxides of rare earth metals are the oxides of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), thulium (Tm), ytterbium (Yb) , Lutetium (Lu).
  • the following rare earth oxides are preferred: La 2 0 3 , Pr 202 and Nd 2 0 3 .
  • the oxides of the rare earth metals can be present in pure form or as a mixture of the oxides of several rare earth metals, as is technically obtained.
  • Inert carriers include, in addition to the Al 2 O 3 , SiO 2 and activated carbon already mentioned, aluminum silicates and magnesium silicates.
  • the palladium content of the catalyst is not critical and can be varied within wide limits. Appropriately is a content of 0.05 to 15% by weight.
  • a content of 0.01 to 10% by weight, based on the support is expedient.
  • the weight ratio of the additional components of the catalyst to the palladium metal can be, for example, between 400: 1 to 1: 150, preferably 50: 1 to 1:10.
  • the catalyst is used, for example, in strands 5 mm in diameter and 10 mm in length or as a powder.
  • the compounds produced by the process of the invention are known and can be used as intermediates for crop protection agents or as active ingredients in known crop protection agents (DE-OS 2752096, 2752135,2656747).
  • a catalyst with the composition of 0.5% by weight Pd, 5% by weight Pr 2 0 3 (95% Pr 2 0 3 , the rest consists of oxides of other rare metals) is placed in a cylindrical reaction tube with a volume of 500 parts by volume Earth metals) filled on Al 2 0 3 as a carrier and heated to 130 ° C. 60 parts per hour of a mixture consisting of 146 parts of 3-phenyl-2-methyl-prop-2-enal (a-methylcinnamaldehyde) and 115 parts of cis-2,6-dimethylmorpholine are passed over this catalyst bed. At the same time, 100,000 parts of hydrogen are passed through the reaction tube in cocurrent at a pressure of 50 bar.
  • a catalyst with the composition of 0.50% by weight of Pd, 0.11% by weight of Zn and 0.10% by weight of Cd on Al 2 O 3 as carrier is introduced into the same apparatus as described in Example 1 and heated to 100 ° C. 60 parts per hour of a mixture consisting of 146 parts of 3-phenyl-2-methyl-prop-2-enal (a-methylcinnamaldehyde) and 115 parts of cis-2,6-dimethylmorpholine are passed over this catalyst bed. At the same time, 10,000 room parts of hydrogen are passed through the reaction tube in cocurrent at a pressure of 50 bar. The product flowing out of the reaction tube is cooled under pressure and then let down. There are 60 parts of crude product per hour, which are purified by distillation. The distillation of 100 parts of crude product leads to 75.5 parts of N- (3 'phenyl-2'-methylpropyl) -cis-2,6-dimethylmorpholine, corresponding to 81% of theory. Th.
  • a mixture of 153 parts of 3-p-tert-butylphenyl-2-methyl-propanal, 70 parts of piperidine, 230 parts of methanol and 20 parts of catalyst, which consists of 0.5% by weight of Pd, 5 % By weight of Nd 2 0 3 to Al 2 0 3 is hydrogenated to constant pressure at 70 ° C. and 50 bar hydrogen pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation. 195 parts of N- (3 ' - (p-tert-butylphenyl) -2'-methyl-propyl) -piperidine are obtained, bp 0.2 117 ° C. The yield is 94% of theory. Th.
  • Example 5 In the apparatus described in more detail in Example 5, a mixture of 153 parts of 4- (p-tert-butylphenyl) butan-2-one, 115 parts of 2,6-dimethylmorpholine (75% cis / 25% trans compound), 270 parts of methanol and 20 parts of the catalyst described in more detail in Example 5 are hydrogenated to constant pressure at 140 ° C. and 50 bar hydrogen pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation.
  • the yield is 82% of theory. Th.
  • a hydrogenation catalyst with the composition of 10% by weight Pd, 0.11% by weight Zn, 0.1% by weight Cd on Al203 at 30 ° C. and normal pressure until the end of the hydrogen uptake.
  • the catalyst is filtered off and the filtrate is worked up by distillation.
  • the autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation.
  • a stirred autoclave of 1000 parts by volume is mixed with a mixture of 153 parts of 3-p-tert-butylphenyl-2-methyl-propanal, 75 parts of hexamethyleneimine, 230 parts of methanol and 20 parts of catalyst, which consists of 0.5% Pd, 5% Pr 2 0 3 , 1% Mn on Al 2 O 3 , filled. Now the mixture is hydrogenated to constant pressure at 90 ° C. and 50 bar hydrogen pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Aralkylaminen durch Umsetzung von Aralkenalen oder Aralkanalen mit sekundären Aminen.The present invention relates to a process for the preparation of aralkylamines by reacting aralkenals or aralkanals with secondary amines.

Es ist bekannt, dass tertiäre Amine durch Umsetzung von sekundären Aminen mit Carbonylverbindungen in Gegenwart von Wasserstoff und einem Hydrierkatalysator erhalten werden können (Houben-Weyl «Methoden der organischen Chemie» 4/2, S. 328 ff, 11/1, S. 602 ff, S. 643 ff). In der deutschen Patentschrift 1179947 wird die Synthese N-alkylierter aromatischer Amine durch reduktive Alkylierung aromatischer Amine an einem Palladium-Silber-Katalysator unter Schonung des aromatischen Systems beschrieben. Nach DE-OS 2118283 kann ebenfalls mit einem Palladium-Silber-Katalysator die Herstellung von tertiären aliphatischen oder cycloaliphatischen Aminen durch Umsetzung von aliphatischen oder cycloaliphatischen Carbonylverbindungen mit sekundären Aminen in Gegenwart von Wasserstoff vorgenommen werden. Der Vorteil dieses Katalysators besteht darin, dass man mit ihm die reduktive Alkylierung von sekundären Aminen mit gesättigten Carbonylverbindungen in hoher Ausbeute und weitgehend frei von Nebenprodukten durchführen kann. Als geeignete Carbonylverbindungen werden insbesondere gesättigte Ketone, wie Aceton, Methyläthylketon, Cyclopentanon, Cyclohexanon und prinzipiell auch Aldehyde, die keine oder nur schwer Adolkondensation eingehen, wie Formaldehyd, Isobutyraldehyd, 2-Äthylhexanal aufgeführt. In der deutschen Patentanmeldung P2 830999 wird die Herstellung von stereoisomerem N-Aralkyl-2,6-dimethylmorpholinen durch Umsetzung von stereoisomeren 2,6-di-Dimethylmorpholinen mit Carbonylverbindungen in Gegenwart von Wasserstoff und einem Palladium-Silber-Katalysator beschrieben.It is known that tertiary amines can be obtained by reacting secondary amines with carbonyl compounds in the presence of hydrogen and a hydrogenation catalyst (Houben-Weyl "Methods of Organic Chemistry" 4/2, p. 328 ff, 11/1, p. 602 ff, p. 643 ff). German patent 1179947 describes the synthesis of N-alkylated aromatic amines by reductive alkylation of aromatic amines over a palladium-silver catalyst while protecting the aromatic system. According to DE-OS 2118283, the production of tertiary aliphatic or cycloaliphatic amines can also be carried out with a palladium-silver catalyst by reacting aliphatic or cycloaliphatic carbonyl compounds with secondary amines in the presence of hydrogen. The advantage of this catalyst is that it can be used for the reductive alkylation of secondary amines with saturated carbonyl compounds in high yield and largely free of by-products. Suitable carbonyl compounds include, in particular, saturated ketones, such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone and, in principle, aldehydes which do not undergo any or only difficult adol condensation, such as formaldehyde, isobutyraldehyde, 2-ethylhexanal. German patent application P2 830999 describes the preparation of stereoisomeric N-aralkyl-2,6-dimethylmorpholines by reacting stereoisomeric 2,6-di-dimethylmorpholines with carbonyl compounds in the presence of hydrogen and a palladium-silver catalyst.

Es wurde nun gefunden, dass man tertiäre Amine der Formel

Figure imgb0001
in der R1 ein Wasserstoffatom, einen aliphatischen Rest mit 1 bis 10 Kohlenstoffatomen, einen cycloaliphatischen Rest mit 5 bis 7 Kohlenstoffatomen, eine Alkoxygruppe mit 1 bis 6 Kohlenstoffatomen, R2, R3 und R4ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 Kohlenstoffatomen, X1, X2, X4 ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 Kohlenstoffatomen, A den Rest
Figure imgb0002
und X5, X6, X7, X8, X9 und X10 ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 Kohlenstoffatomen und n die Zahlen 1, 2, 3 oder 4 bedeutet, durch Umsetzung von sekundären Aminen der Formel II
Figure imgb0003
in der X1, X2, X3, X4 und A die oben angegebene Bedeutung haben, mit Carbonylverbindungen der Formel 111
Figure imgb0004
in der R1, R2, R3 die angegebene Bedeutung besitzen und die gestrichelte Bindung eine Doppelbindung oder eine einfache Bindung ist in einfacher Weise erhält, wenn man die Umsetzung in Gegenwart von Wasserstoff und einem Hydrierkatalysator durchführt, der Palladium im Gemisch mit Zink, Cadmium, Mangan und/oder einem Oxid der Seltenen Erdmetalle auf einem inerten Träger enthält. Der inerte Träger kann beispielsweise aus Aluminiumoxid, Kieselsäure oder Aktivkohle bestehen. Man führt die Umsetzung beispielsweise bei Temperaturen zwischen 10 und 200°C durch. Es kann drucklos oder bei Drucken bis zu 300 bar gearbeitet werden.It has now been found that tertiary amines of the formula
Figure imgb0001
 in which R 1 is a hydrogen atom, an aliphatic radical having 1 to 10 carbon atoms, a cycloaliphatic radical having 5 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, R 2 , R 3 and R 4 are a hydrogen atom or an alkyl radical having 1 to 4 Carbon atoms, X 1 , X 2 , X 4 is a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms, A the rest
Figure imgb0002
 and X5, X6, X7, X8, X9 and X 10 represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms and n represents the numbers 1, 2, 3 or 4, by reacting secondary amines of the formula II
Figure imgb0003
 in which X 1 , X 2 , X 3 , X 4 and A have the meaning given above, with carbonyl compounds of the formula 111
Figure imgb0004
 in which R 1 , R 2 , R 3 have the meaning given and the dashed bond is a double bond or a single bond can be obtained in a simple manner if the reaction is carried out in the presence of hydrogen and a hydrogenation catalyst which comprises palladium in a mixture with zinc, Contains cadmium, manganese and / or an oxide of rare earth metals on an inert carrier. The inert carrier can consist, for example, of aluminum oxide, silica or activated carbon. The reaction is carried out, for example, at temperatures between 10 and 200 ° C. It can be operated without pressure or at pressures up to 300 bar.

Der Vorteil des erfindungsgemässen Verfahrens besteht darin, dass insbesondere empfindliche Carbonylverbindungen, wie a, ß-ungesättigte Aldehyde oder Ketone, die die Amine an die Doppelbindungen anlagern könnten und dann keine einheitlichen Endprodukte ergeben könnten, oder Aldehyde bzw. Ketone, die Aldolkondensationen eingehen könnten, verwendet werden können und einheitliche Endprodukte ergeben.The advantage of the process according to the invention is that in particular sensitive carbonyl compounds, such as α, β-unsaturated aldehydes or ketones, which the amines could attach to the double bonds and then could not give rise to uniform end products, or aldehydes or ketones which could undergo aldol condensation, can be used and result in uniform end products.

Ein weiterer Vorteil des erfindungsgemässen Verfahrens ist darin zu sehen, dass die gewünschten Endprodukte der Formel aufgrund der hohen Selektivität der verwendeten Katalysatoren in sehr sauberer Form anfallen. So werden die bei diesem Reaktionstyp zu erwartenden Nebenprodukte, wie beispielsweise die durch Hydrierung aus den Carbonylverbindungen zu erwartenden Alkohole der Formel

Figure imgb0005
oder ungesättigte Amine der Formeln
Figure imgb0006
Figure imgb0007
kaum erhalten.Another advantage of the process according to the invention is that the desired end products of the formula are obtained in a very clean form due to the high selectivity of the catalysts used. The by-products to be expected in this type of reaction, such as, for example, the alcohols of the formula to be expected from the carbonyl compounds by hydrogenation
Figure imgb0005
 or unsaturated amines of the formulas
Figure imgb0006
Figure imgb0007
 hardly received.

Bei der Verwendung eines weniger selektiven Katalysators, beispielsweise des bekannten Palladium-Silber-Katalysators (DE-PS 1179947, DE-OS 2118283) werden die angegebenen Nebenprodukte in erheblich grösserer Menge erhalten (vgl. Beispiele 13 + 18).When using a less selective catalyst, for example the known palladium-silver catalyst (DE-PS 1179947, DE-OS 2118283), the stated by-products are obtained in a considerably larger amount (cf. Examples 13 + 18).

Beim Arbeiten nach dem erfindungsgemässen Verfahren hat man weiterhin den Vorteil, dass sterisch einheitliche Produkte erhalten werden, wenn sterisch einheitliche Produkte als Ausgangsprodukte verwendet werden. Die an Hydrierkatalysatoren oft autretenden Isomerisierungen (Houben-Weyl, «Methoden der Organischen Chemie», 4/2, S. 276 bis 283) werden hier nicht beobachtet.When working according to the method according to the invention, there is also the advantage that sterically uniform products are obtained if sterically uniform products are used as starting products. The isomerizations that often occur in hydrogenation catalysts (Houben-Weyl, “Methods of Organic Chemistry”, 4/2, pp. 276 to 283) are not observed here.

Die Aminkomponente kann nach dem erfindungsgemässen Verfahren in stöchiometrischer Menge, bezogen auf die Carbonylverbindung oder in einem bis zu 10fach molaren Überschuss angewendet werden.The amine component can be used in a stoichiometric amount, based on the carbonyl compound, or in an up to 10-fold molar excess by the process according to the invention.

Als Ausgangsprodukte der Formel III kommen beispielsweise folgende Carbonylverbindungen in Frage:

  • 3-Phenyl-2-methyl-prop-2-enal, 3-Phenyl-2-methyl-propanal, 3-Phenyl-3-methyl-prop-2-enal, 3-Phenyl-3-methyl-propanal, 4-Phenyl-but-3-en-2-on, 4-Phenyl-butan-2-on, 3-(4'-Methyl-phenyl)-2-methyl-prop-2-enal, 3-(4'-Methylphenyl)-2-methylpropanal, 3-(4'lsopropylphenyl)-2-methyl-prop-2-enal, 3-(4'-lsopropylphenyl)-2-methyl-propanal, 3-(4'-Tertiärbutylphenyl)-2-methyl-prop-2-enal, 3-(4'-Tertiärbutylphenyl)-2-methyl-propanal, 3-Phenyl-2-äthyl-prop-2-enal, 3-Phenyl-2-äthylpropanal, 3-Phenyl-2-isopropyl- prop-2-enal, 3-Phenyl-2-ispopropyl-propanal, 3-)4'-Isopropylphenyl)-3-methyl-prop-2-enal, 3-(4'-lsopropylphenyl)-3-methylpropanal, 3-(4'-Tertiärbutylphenyl)-3-methyl-prop-2-enal, 3-(4'-Tertiärbutylphenyl)-3-methyl-propanal, 4-(4'-Tertiärbutylphenyl)-but-3-en-2-on, 4-(4'-Tertiär- butylphenyl)-buten-2-on, 3-(4'-Methoxyphenyl)-2-methyl-prop-2-enal, 3-(4'-Methoxyphenyl)-2-methyl-propanal, 3-(4' -lsopropoxyphenyl)-2-methyl-prop-2-enal, 3-(4'-Isopropopoxyphenyl)-2-methyl-propanal, 3-(4'-Cyclohexylphenyl)-2-methyl-prop-2-enal, 3-(4' -Cyclohexylphenyl)-2-methyl-propanal, 3-(4' -Cyclopentylphenyl)-2-methyl-prop-2-enal, 3-(4'-Cyclopentylphenyl)-2-methyl-propanal.
The following carbonyl compounds, for example, are suitable as starting products of the formula III:
  • 3-phenyl-2-methyl-prop-2-enal, 3-phenyl-2-methyl-propanal, 3-phenyl-3-methyl-prop-2-enal, 3-phenyl-3-methyl-propanal, 4- Phenyl-but-3-en-2-one, 4-phenyl-butan-2-one, 3- (4'-methylphenyl) -2-methyl-prop-2-enal, 3- (4'-methylphenyl ) -2-methylpropanal, 3- (4'-isopropylphenyl) -2-methyl-prop-2-enal, 3- (4'-isopropylphenyl) -2-methyl-propanal, 3- (4'-tertiary butylphenyl) -2- methyl-prop-2-enal, 3- (4'-tertiary-butylphenyl) -2-methyl-propanal, 3-phenyl-2-ethyl-prop-2-enal, 3-phenyl-2-ethyl-propanal, 3-phenyl-2 -isopropyl-prop-2-enal, 3-phenyl-2-isopropyl-propanal, 3-) 4'-isopropylphenyl) -3-methyl-prop-2-enal, 3- (4'-isopropylphenyl) -3-methylpropanal , 3- (4'-tertiary-butylphenyl) -3-methyl-prop-2-enal, 3- (4'-tertiary-butylphenyl) -3-methyl-propanal, 4- (4'-tertiary-butylphenyl) -but-3-en- 2-one, 4- (4'-tertiary-butylphenyl) buten-2-one, 3- (4'-methoxyphenyl) -2-methyl-prop-2-enal, 3- (4'-methoxyphenyl) -2 -methyl-propanal, 3- (4'-isopropoxyphenyl) -2-methyl-prop-2-enal, 3- (4'-isopropopoxyphenyl) -2-methyl-propanal, 3- (4'-cyclohexylphe nyl) -2-methyl-prop-2-enal, 3- (4 '-cyclohexylphenyl) -2-methyl-propanal, 3- (4' -cyclopentylphenyl) -2-methyl-prop-2-enal, 3- ( 4'-cyclopentylphenyl) -2-methyl-propanal.

Die Herstellung der bekannten Ausgangsprodukte III kann durch Aldolkondensation von entsprechend substituierten Benzaldehyden mit aliphatischen Aldehyden bzw. Ketonen erfolgen. Die hydrierten Verbindungen erhält man aus den ungesättigten Produkten durch Partialhydrierung der Kohlenstoff-Kohlenstoff-Doppelbindung (US-PS 2 976 321).The known starting products III can be prepared by aldol condensation of appropriately substituted benzaldehydes with aliphatic aldehydes or ketones. The hydrogenated compounds are obtained from the unsaturated products by partial hydrogenation of the carbon-carbon double bond (US Pat. No. 2,976,321).

Als tertiäre Amine der Formel II, die nach dem erfindungsgemässen Verfahren umgesetzt werden können, sind beispielsweise folgende Verbindungen zu nennen:

  • Pyrrolidin, Piperidin, 2-Methylpiperidin; 3-Methylpiperidin, 4-Methylpiperidin, 2,6-Dimethylpiperidin, 3,5-Dimethylpiperidin, 4-Äthylpiperidin, Morpholin, 2-Methylmorpholin, 2-Äthylmorpholin, 3-Methylmorpholin, 2,6-Dimethylmorpholin, 3,5-Dimethylmorpholin, 2,5-Dimethylmorpholin, 2,6-Diäthylmorpholin, Piperazin, 1-Methylpiperazin, Hexamethylenimin, 2,3-Dimethylhexamethylenimin, 3,5,5-Trimethylhexamethylenimin und 3,3,5-Trimethylhexamethylenimin.
The following compounds are examples of tertiary amines of the formula II which can be reacted by the process according to the invention:
  • Pyrrolidine, piperidine, 2-methylpiperidine; 3-methylpiperidine, 4-methylpiperidine, 2,6-dimethylpiperidine, 3,5-dimethylpiperidine, 4-ethylpiperidine, morpholine, 2-methylmorpholine, 2-ethylmorpholine, 3-methylmorpholine, 2,6-dimethylmorpholine, 3,5-dimethylmorpholine, 2,5-dimethylmorpholine, 2,6-diethylmorpholine, piperazine, 1-methylpiperazine, hexamethyleneimine, 2,3-dimethylhexamethyleneimine, 3,5,5-trimethylhexamethyleneimine and 3,3,5-trimethylhexamethyleneimine.

Die Umsetzung kann ohne Lösungsmittel oder in Anwesenheit von Lösungsmitteln, die unter den Reaktionsbedingungen inert sind, durchgeführt werden. Als Lösungsmittel kommen beispielsweise in Frage:

  • Methanol, Äthanol, Propanol, Tetrahydrofuran, Dioxan, Anisol, Äthylenglykol-monomethyläther, 1,2-Dimethoxyäthan, Methyl-tert.-butyläther, Cyclohexylmethyläther, Di-n-butyläther, Toluol, Cyclohexan.
The reaction can be carried out without a solvent or in the presence of solvents which are inert under the reaction conditions. Examples of suitable solvents are:
  • Methanol, ethanol, propanol, tetrahydrofuran, dioxane, anisole, ethylene glycol monomethyl ether, 1,2-dimethoxyethane, methyl tert-butyl ether, cyclohexyl methyl ether, di-n-butyl ether, toluene, cyclohexane.

Die Umsetzung ist sowohl kontinuierlich als auch diskontinuierlich - bevorzugt in flüssiger Phase - durchführbar.The reaction can be carried out both continuously and batchwise, preferably in the liquid phase.

Das nach dem Verfahren der Erfindung verwendete Katalysatorsystem enthält einerseits Palladium als Hydriermetall und andererseits die Zusatzkomponenten Zink, Cadium, Mangan oder ein Oxid der Seltenen Erdmetalle oder Gemische von Oxiden der Seltenen Erdmetalle, wobei die genannten Zusatzkomponenten allein oder im Gemisch miteinander neben dem Palladium vorliegen können. Diese Katalysatorzusätze haben eine Erhöhung der Selektivität des Hydrierkatalysators zur Folge.The catalyst system used by the process of the invention contains, on the one hand, palladium as the hydrogenation metal and, on the other hand, the additional components zinc, cadium, manganese or an oxide of the rare earth metals or mixtures of oxides of the rare earth metals, it being possible for the additional components mentioned to be present alone or in a mixture with one another in addition to the palladium . These catalyst additives result in an increase in the selectivity of the hydrogenation catalyst.

Als Oxide der Seltenen Erdmetalle bezeichnen wir erfindungsgemäss die Oxide von Lanthan (La), Cer (Ce), Praseodym (Pr), Neodym (Nd), Samarium (Sm), Europium (Eu), Thulium (Tm), Ytterbium (Yb), Lutetium (Lu). Bevorzugt seien folgende Oxide der Seltenen Erden genannt: La203, Pr202 und Nd203.According to the invention, the oxides of rare earth metals are the oxides of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), thulium (Tm), ytterbium (Yb) , Lutetium (Lu). The following rare earth oxides are preferred: La 2 0 3 , Pr 202 and Nd 2 0 3 .

In dem erfindungsgemäss verwendeten Katalysatorsystem können die Oxide der Seltenen Erdmetalle in reiner Form oder als Gemisch der Oxide mehrerer Seltener Erdmetalle, so wie es technisch anfällt, vorliegen.In the catalyst system used according to the invention, the oxides of the rare earth metals can be present in pure form or as a mixture of the oxides of several rare earth metals, as is technically obtained.

Als inerte Träger sind beispielsweise neben den bereits genannten Al2O3, SiO2 und Aktivkohle noch Aluminiumsilikate und Magnesiumsilikate zu nennen.Inert carriers include, in addition to the Al 2 O 3 , SiO 2 and activated carbon already mentioned, aluminum silicates and magnesium silicates.

Der Palladiumgehalt des Katalysators, bezogen auf das Trägermaterial, ist nicht kritisch und kann in weiten Grenzen variiert werden. Zweckrnässig ist ein Gehalt von 0,05 bis 15 Gew.-%. Für die Zusatzkomponenten des Katalysators (Zink, Cadmium, Mangan, Oxide der Seltenen Erdmetalle) ist ein Gehalt von 0,01 bis 10 Gew.-% - bezogen auf den Träger - zweckmässig. Das Gewichtsverhältnis der Zusatzkomponenten des Katalysators zu dem Palladiummetall kann beispielsweise zwischen 400:1 bis 1:150, bevorzugt bei 50:1 bis 1:10 liegen. Man verwendet den Katalysator beispielsweise in Strängen von 5 mm Durchmesser und 10 mm Länge oder als Pulver.The palladium content of the catalyst, based on the support material, is not critical and can be varied within wide limits. Appropriately is a content of 0.05 to 15% by weight. For the additional components of the catalyst (zinc, cadmium, manganese, oxides of rare earth metals), a content of 0.01 to 10% by weight, based on the support, is expedient. The weight ratio of the additional components of the catalyst to the palladium metal can be, for example, between 400: 1 to 1: 150, preferably 50: 1 to 1:10. The catalyst is used, for example, in strands 5 mm in diameter and 10 mm in length or as a powder.

Die nach dem Verfahren der Erfindung hergestellten Verbindungen sind bekannt und können als Zwischenprodukte für Pflanzenschutzmittel oder als Wirkstoffe in bekannten Pflanzenschutzmitteln Verwendung finden (DE-OS 2752096, 2752135,2656747).The compounds produced by the process of the invention are known and can be used as intermediates for crop protection agents or as active ingredients in known crop protection agents (DE-OS 2752096, 2752135,2656747).

Die in den folgenden Beispielen genannten Teile bedeuten Gew.-Teile, Raumteile verhalten sich zu ihnen wie Liter zu Kilogramm.The parts mentioned in the following examples mean parts by weight, room parts behave like liters to kilograms.

Beispiel 1example 1

In ein zylindrisches Reaktionsrohr mit einem Volumen von 500 Raumteilen wird ein Katalysator mit der Zusammensetzung von 0,5 Gew.-% Pd, 5 Gew.-% Pr203 (95%iges Pr203, Rest besteht aus Oxiden anderer Seltener Erdmetalle) auf AI203 als Träger eingefüllt und auf 130°C erhitzt. Über dieses Katalysatorbett werden stündlich 60 Teile einer Mischung geführt, die aus 146 Teilen 3-Phenyl-2-methyl-prop-2-enal (a-Methylzimtaldehyd) und 115 Teilen cis-2,6-Dimethylmorpholin besteht. Gleichzeitig werden 100000 Raumteile Wasserstoff bei einem Druck von 50 bar durch das Reaktionsrohr im Gleichstrom hindurchgeleitet. Das aus dem Reaktionsrohr herausfliessende Reaktionsprodukt wird unter Druck abgekühlt und dann entspannt. Es fallen hierbei stündlich 60 Teile Rohprodukt an, die destillativ gereinigt werden. Die Destillation von 100 Teilen Rohprodukt führt zu 77,5 Teilen N-(3'-Phenyl-2'-methylpropyl)-cis-2,6-dimethylmorpholin, Kp0,01 = 95°C. Das entspricht einer Ausbeute von 83% d. Th.A catalyst with the composition of 0.5% by weight Pd, 5% by weight Pr 2 0 3 (95% Pr 2 0 3 , the rest consists of oxides of other rare metals) is placed in a cylindrical reaction tube with a volume of 500 parts by volume Earth metals) filled on Al 2 0 3 as a carrier and heated to 130 ° C. 60 parts per hour of a mixture consisting of 146 parts of 3-phenyl-2-methyl-prop-2-enal (a-methylcinnamaldehyde) and 115 parts of cis-2,6-dimethylmorpholine are passed over this catalyst bed. At the same time, 100,000 parts of hydrogen are passed through the reaction tube in cocurrent at a pressure of 50 bar. The reaction product flowing out of the reaction tube is cooled under pressure and then let down. There are 60 parts of crude product per hour, which are purified by distillation. The distillation of 100 parts of crude product leads to 77.5 parts of N- (3'-phenyl-2 ' -methylpropyl) -cis-2,6-dimethylmorpholine, bp 0.01 = 95 ° C. This corresponds to a yield of 83% of theory. Th.

Beispiel 2Example 2

In die gleiche Apparatur wie in Beispiel 1 beschrieben wird ein Katalysator mit der Zusammensetzung von 0,50 Gew.-% Pd, 0,11 Gew.-% Zn und 0,10 Gew.-% Cd auf AI203 als Träger eingefüllt und auf 100°C erhitzt. Über dieses Katalysatorbett werden stündlich 60 Teile einer Mischung geführt, die aus 146 Teilen 3-Phenyl-2-methyl- prop-2-enal (a-Methylzimtaldehyd) und 115 Teilen cis-2,6-Dimethylmorpholin besteht. Gleichzeitig werden 10000 Raumteile Wasserstoff bei einem Druck von 50 bar durch das Reaktionsrohr im Gleichstrom hindurchgeleitet. Das aus dem Reaktionsrohr herausfliessende Produkt wird unter Druck abgekühlt und dann entspannt. Es fallen hierbei stündlich 60 Teile Rohprodukt an, die destillativ gereinigt werden. Die Destillation von 100 Teilen Rohprodukt führt zu 75,5 Teilen N-(3' Phenyl-2'-methylpropyl)-cis-2,6-dimethylmorpholin, entspr. 81% d. Th.A catalyst with the composition of 0.50% by weight of Pd, 0.11% by weight of Zn and 0.10% by weight of Cd on Al 2 O 3 as carrier is introduced into the same apparatus as described in Example 1 and heated to 100 ° C. 60 parts per hour of a mixture consisting of 146 parts of 3-phenyl-2-methyl-prop-2-enal (a-methylcinnamaldehyde) and 115 parts of cis-2,6-dimethylmorpholine are passed over this catalyst bed. At the same time, 10,000 room parts of hydrogen are passed through the reaction tube in cocurrent at a pressure of 50 bar. The product flowing out of the reaction tube is cooled under pressure and then let down. There are 60 parts of crude product per hour, which are purified by distillation. The distillation of 100 parts of crude product leads to 75.5 parts of N- (3 'phenyl-2'-methylpropyl) -cis-2,6-dimethylmorpholine, corresponding to 81% of theory. Th.

Beispiel 3Example 3

In der gleichen Apparatur und mit dem gleichen Katalysator, wie in Beispiel 1 beschrieben, wird bei einer stündlichen Zufuhr von 120 Teilen einer Mischung, die aus 261 Teilen Methanol, 146 Teilen 3-Phenyl-2-methyl-prop-2-enal (a-Methylzimtaldehyd) und 115 Teilen 2,6-Dimethyimorpholin mit 75 Gew.-% cis-und 25 Gew.-% trans-Verbindung besteht, die Umsetzung bei 120°C vorgenommen. Gleichzeitig mit der vorher genannten Mischung werden 100000 Raumteile Wasserstoff bei einem Druck von 50 bar durch das Reaktionsrohr im Gleichstrom hindurch geleitet. Das aus dem Reaktionsrohr herausfliessende Reaktionsprodukt wird unter Druck abgekühlt und dann entspannt. Es fallen hierbei stündlich 120 Teile Rohprodukt an, die destillativ gereinigt werden. Die Destillation von 200 Teilen Rohprodukt führt zu 80,5 Teilen N-(3'Phenyi-2'-methylpropyl)-2,6-dimethylmorpholin mit 75 Gew.-% cis- und 25 Gew.-% trans-Verbindung, KP12 = 155 bis 157°C. Das entspricht einer Ausbeute von 86% d. Th.In the same apparatus and with the same catalyst as described in Example 1, with an hourly feed of 120 parts of a mixture consisting of 261 parts of methanol, 146 parts of 3-phenyl-2-methyl-prop-2-enal (a -Methylzimtaldehyd) and 115 parts of 2,6-dimethyimorpholine with 75 wt .-% cis and 25 wt .-% trans compound, the reaction is carried out at 120 ° C. Simultaneously with the aforementioned mixture, 100,000 parts of hydrogen are passed through the reaction tube in cocurrent at a pressure of 50 bar. The reaction product flowing out of the reaction tube is cooled under pressure and then let down. There are 120 parts of crude product per hour, which are purified by distillation. The distillation of 200 parts of crude product leads to 80.5 parts of N- (3'phenyi-2'-methylpropyl) -2,6-dimethylmorpholine with 75% by weight cis and 25% by weight trans compound, KP 12 = 155 to 157 ° C. This corresponds to a yield of 86% of theory. Th.

Beispiel 4Example 4

In der gleichen Apparatur und mit dem gleichen Katalysator wie in Beispiel 1 beschrieben, wird bei einer stündlichen Zufuhr von 120 Teilen einer Mischung, die aus 317 Teilen Methanol, 202 Teilen 3-p-Tertiärbutylphenyl-2-methyl-prop-2- enal und 115 Teilen cis-2,6-Dimethylmorpholin besteht, die Umsetzung bei 130°C vorgenommen. Gleichzeitig mit der vorher genannten Mischung werden 100000 Raumteile Wasserstoff bei einem Druck von 50 bar durch das Reaktionsrohr im Gleichstrom hindurchgeleitet. Das aus dem Reaktionsrohr herausfliessende Reaktionsprodukt wird unter Druck abgekühlt und dann entspannt. Es fallen hierbei stündlich 120 Teile Rohprodukt an, die destillativ gereinigt werden. Die Destillation von 200 Teilen Rohprodukt führt zu 88,5 Teilen N-(3'-(p-Tertiärbutylphenyl)-2'-methyl-propyl)-cis-2,6-dimethylmorpholin, KP18 = 206°C. Das entspricht einer Ausbeute von 92,5% d. Th.In the same apparatus and with the same catalyst as described in Example 1, with an hourly feed of 120 parts of a mixture consisting of 317 parts of methanol, 202 parts of 3-p-tertiary butylphenyl-2-methyl-prop-2-enal and There are 115 parts of cis-2,6-dimethylmorpholine, the reaction is carried out at 130 ° C. Simultaneously with the aforementioned mixture, 100,000 parts of hydrogen are passed through the reaction tube in cocurrent at a pressure of 50 bar. The reaction product flowing out of the reaction tube is cooled under pressure and then let down. There are 120 parts of crude product per hour, which are purified by distillation. The distillation of 200 parts of crude product leads to 88.5 parts of N- (3 '- (p-tert-butylphenyl) -2'-methyl-propyl) -cis-2,6-dimethylmorpholine, KP 18 = 206 ° C. This corresponds to a yield of 92.5% of theory. Th.

Beispiel 5Example 5

In einem Rührautoklaven von 1000 Raumteilen Inhalt wird eine Mischung aus 153 Teilen 3-p-Ter- tiärbutylphenyl-2-methyl-propanal, 70 Teilen Piperidin, 230Teilen Methanol und 20 Teilen Katalysator, der aus 0,5 Gew.-% Pd, 5 Gew.-% Nd203 auf AI203 besteht, bei 70°C und 50 bar Wasserstoffdruck bis zur Druckkonstanz hydriert. Anschliessend lässt man den Autoklaven abkühlen, filtriert den Katalysator ab und reinigt das Filtrat destillativ. Man erhält 195 Teile N-(3'-(p-Tertiär- butylphenyl)-2'-methyl-propyl)-piperidin, Kp0,2 = 117°C. Die Ausbeute beträgt 94% d. Th.A mixture of 153 parts of 3-p-tert-butylphenyl-2-methyl-propanal, 70 parts of piperidine, 230 parts of methanol and 20 parts of catalyst, which consists of 0.5% by weight of Pd, 5 % By weight of Nd 2 0 3 to Al 2 0 3 is hydrogenated to constant pressure at 70 ° C. and 50 bar hydrogen pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation. 195 parts of N- (3 ' - (p-tert-butylphenyl) -2'-methyl-propyl) -piperidine are obtained, bp 0.2 = 117 ° C. The yield is 94% of theory. Th.

Beispiel 6Example 6

In der in Beispiel 5 näher beschriebenen Apparatur wird ein Gemisch aus 153 Teilen 4-(p-Terti- ärbutylphenyl)-butan-2-on, 115 Teilen 2,6-Dimethylmorpholin (75% cis-/25% trans-Verbindung), 270 Teilen Methanol und 20 Teilen des unter Beispiel 5 näher beschriebenen Katalysators bei 140°C und 50 bar Wasserstoffdruck bis zur Druckkonstanz hydriert. Anschliessend lässt man den Autoklaven abkühlen, filtriert den Katalysator ab und reinigt das Filtrat destillativ. Man erhält 195,5 Teile N-(4'-(p-Tertiärbutylphenyl)-but-2'-yl)-2,6-dimethylmorpholin (75% cis-/25% trans-Verbindung), Kp0,01 = 143°C. Die Ausbeute beträgt 86% d. Th.In the apparatus described in more detail in Example 5, a mixture of 153 parts of 4- (p-tert-butylphenyl) butan-2-one, 115 parts of 2,6-dimethylmorpholine (75% cis / 25% trans compound), 270 parts of methanol and 20 parts of the catalyst described in more detail in Example 5 are hydrogenated to constant pressure at 140 ° C. and 50 bar hydrogen pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation. 195.5 parts of N- (4 '- (p-tertiary-butylphenyl) but-2'-yl) -2,6-dimethylmorpholine (75% cis / 25% trans compound), bp 0.01 = 143 ° C. The yield is 86% of theory. Th.

Beispiel 7Example 7

Man verfährt analog Beispiel 5, verwendet aber als Aminkomponente 2,2,4-Trimethylazetidin. Hierbei fällt als Endprodukt N-(3'-(p-Tertiärbutyl- phenyl)-2'-methyl-propyl)-2,2,4-trimethyl-azeti- din an, Kp0,3 = 134°C. Die Ausbeute beträgt 93% d. Th.The procedure is analogous to Example 5, but 2,2,4-trimethylazetidine is used as the amine component. The end product obtained is N- (3 '- (p-tert-butylphenyl) -2'-methyl-propyl) -2,2,4-trimethyl-acetidine, bp 0.3 = 134 ° C. The yield is 93% of theory. Th.

Beispiel 8Example 8

Man verfährt analog Beispiel 5, verwendet aber als Ausgangsstoff 3-p-Tertiärbutylphenyl-2-methyl-prop-2-enal als Carbonylkomponente und 2,3-Dimethylhexamethylenimin als Aminkomponente. Als Endprodukt wird hierbei N-(3'-(p-Ter- tiärbutylphenyl)-2'-methyl-propyl)-2,3-dimethylhexamethylenimin, Kp0,01 = 144°C erhalten. Die Ausbeute beträgt 95% d. Th.The procedure is analogous to Example 5, but the starting material used is 3-p-tertiary-butylphenyl-2-methyl-prop-2-enal as the carbonyl component and 2,3-dimethylhexamethyleneimine as the amine component. The end product obtained is N- (3 ' - (p-tert-butylphenyl) -2'-methyl-propyl) -2,3-dimethylhexamethyleneimine, bp 0.01 = 144 ° C. The yield is 95% of theory. Th.

Beispiel 9Example 9

Man verfährt analog Beispiel 5, verwendet aber als Aminkomponente Pyrrolidin. Als Endprodukt fällt N-(3'-(p-Tertiärbutylphenyl)-2'-methyl-propyl)-pyrrolidin an, Kpo,3 = 115 °C. Die Ausbeute beträgt 96% d. Th.The procedure is analogous to Example 5, but pyrrolidine is used as the amine component. The end product is N- (3 '- (p-tert-butylphenyl) -2'-methyl-propyl) -pyrrolidine, Kp o , 3 = 115 ° C. The yield is 96% of theory. Th.

Beispiel 10Example 10

In einem Rührautoklaven von 1000 Raumteilen Inhalt wird eine Mischung aus 190 Teilen 3-p-lso- propylphenyl-3-methyi-propanal, 111 Teilen 2-Methylmorpholin, 300 Teilen Methanol und 20 Teilen Katalysator, der aus 0,5 Gew.-% Pd, 0,11 Gew.-% Zn und 0,1 Gew.-% Cd auf A1203 besteht, bei 120°C und 50 bar Wasserstoffdruck bis zur Druckkonstanz hydriert. Anschliessend lässt man den Autoklaven abkühlen, filtriert den Katalysator ab und reinigt das Filtrat destillativ. Man erhält 266 Teile N-(3'-(p-lsopropylphenyl)-3'-methylpropyl)-2-methylmorpholin, Kp0,05 = 122°C. Die Ausbeute beträgt 82% d. Th.A mixture of 190 parts of 3-p-isopropylphenyl-3-methyl propanal, 111 parts of 2-methylmorpholine, 300 parts of methanol and 20 parts of catalyst, which consists of 0.5% by weight, Pd, 0.11% by weight Zn and 0.1% by weight Cd on A1 2 03, hydrogenated at 120 ° C. and 50 bar hydrogen pressure to constant pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation. 266 parts of N- (3 '- (p-isopropylphenyl) -3'-methylpropyl) -2-methylmorpholine, bp 0.05 = 122 ° C., are obtained. The yield is 82% of theory. Th.

Beispiel 11Example 11

Man verfährt analog Beispiel 10, verwendet aber als Ausgangsstoff 3-p-Methoxyphenyl-2-methyl-propanal als Carbonylkomponente und cis-2,6-Dimethylmorpholin als Aminkomponente. Dies führt zu N-(3'-p-Methoxyphenyl)-2'-methylpropyl)-cis-2,6-dimethylmorpholin, Kp0,1 = 129°C als Endprodukt. Die Ausbeute beträgt 82% d. Th.The procedure is analogous to Example 10, but the starting material used is 3-p-methoxyphenyl-2-methylpropanal as the carbonyl component and cis-2,6-dimethylmorpholine as the amine component. This leads to N- (3'-p-methoxyphenyl) -2'-methylpropyl) -cis-2,6-dimethylmorpholine, bp 0.1 = 129 ° C as the end product. The yield is 82% of theory. Th.

Beispiel 12Example 12

In einer Rührapparatur mit einem Inhalt von 2000 Raumteilen wird ein Gemisch aus 101 Teilen 3-p-Tertiärbutylphenyl-2-methyl-prop-2-enal und 61 Teilen cis-2,6-Dimethylmorpholin, das in 900 Teilen Methanol gelöst ist, in Gegenwart von 5 Teilen eines Hydrierkatalysators mit der Zusammensetzung von 10 Gew.-% Pd, 0,11 Gew.-% Zn, 0,1 Gew.-% Cd auf AI203 bei 30°C und Normaldruck bis zum Ende der Waserstoffaufnahme hydriert. Der Katalysator wird abfiltriert und das Filtrat destillativ aufgearbeitet. Hierbei werden 141 Teile N-(3'-(p-Tertiärbutylphenyl)-2'-methyl-propyl)-cis-1,6-dimethylmorpholin, Kp18 = 206°C erhalten. Das entspricht einer Ausbeute von 93%.A mixture of 101 parts of 3-p-tertiary-butylphenyl-2-methyl-prop-2-enal and 61 parts of cis-2,6-dimethylmorpholine, which is dissolved in 900 parts of methanol, is dissolved in a stirring apparatus with a content of 2000 parts by volume The presence of 5 parts of a hydrogenation catalyst with the composition of 10% by weight Pd, 0.11% by weight Zn, 0.1% by weight Cd on Al203 at 30 ° C. and normal pressure until the end of the hydrogen uptake. The catalyst is filtered off and the filtrate is worked up by distillation. This gives 141 parts of N- (3 '- (p-tert-butylphenyl) -2'-methyl-propyl) -cis-1,6-dimethylmorpholine, bp 18 = 206 ° C. This corresponds to a yield of 93%.

Beispiel 13 - VergleichsbeispielExample 13 - Comparative Example

Mit einem Katalysator der Zusammensetzung von 0,36 Gew.-% Pd, 4,8 Gew.-% Ag und 1,05 Gew.-% Mn auf Si02 wird völlig analog Beispiel 1 mit denselben Einsatzstoffen und unter denselben Reaktionsbedingungen gearbeitet. Das hierbei erhaltene Reaktionsprodukt hat nach gaschromatographischer Analyse folgende Zusammensetzung:

  • 22 Gew.-% N-(3'-Phenyl-2'-methyl-propyl)-cis-2,6-dimethylmorpholin, 14 Gew.-% N-(3' -Phenyl-2'-methyl-prop-2'-enyl)-cis-2,6-dimethylmorpholin, 36,2 Gew.-% 3-Phenyl-2-methylpropanol und 27,8 Gew.-% cis-2,6 Dimethylmorpholin.
With a catalyst having the composition of 0.36% by weight of Pd, 4.8% by weight of Ag and 1.05% by weight of Mn on SiO 2 , the same starting materials and the same reaction conditions are used, completely analogously to Example 1. The reaction product obtained in this way has the following composition according to gas chromatographic analysis:
  • 22% by weight of N- (3'-phenyl-2'-methyl-propyl) -cis-2,6-dimethylmorpholine, 14% by weight of N- (3'-phenyl-2'-methyl-prop-2 '-enyl) -cis-2,6-dimethylmorpholine, 36.2% by weight 3-phenyl-2-methylpropanol and 27.8% by weight cis-2,6-dimethylmorpholine.

Beispiel 14Example 14

In einem Rührautoklaven von 5000 Raumteilen Inhalt wird eine Mischung aus 2500 Raumteilen Methanol, 366 Teilen cis-2,6-Dimethylmorpholin, 606 Teilen 3-p-Tertiärbutyl-phenyl-2-methyl- prop-2-enal und 35 Teilen Katalysator, der aus 0,5 Gew.-% Pd, 5 Gew.-% Pr203, 1 Gew.-% Mn und als Rest Al2O3 besteht, stufenweise zunächst bei 50° und 50 bar Wasserstoffdruck, dann bei 90°C und 50 bar Wasserstoffdruck, zum Schluss bei 120°C und 50 bar Wasserstoffdruck, bis zur Druckkonstanz hydriert. Anschliessend lässt man den Autoklaven abkühlen, filtriert den Katalysator ab und reinigt das Filtrat destillativ. Man erhält 856 Teile N-(3'-p-Tertiärbutylphenyl-2'-methyl-propyl)-cis-2,6-dimethylmorpholin, Kp24 mbar = 206°C. Das entspricht einer Ausbeute von 94% d. Th. (bez. auf 3-p-tertiärbutylphenyl-2-methyl-prop-2- enal).A mixture of 2500 parts by volume of methanol, 366 parts of cis-2,6-dimethylmorpholine, 606 parts of 3-p-tertiary-butyl-phenyl-2-methyl-prop-2-enal and 35 parts of catalyst, the consists of 0.5 wt.% Pd, 5 wt.% Pr 2 0 3 , 1 wt.% Mn and the remainder Al 2 O 3 , gradually at 50 ° and 50 bar hydrogen pressure, then at 90 ° C and 50 bar hydrogen pressure, at the end at 120 ° C and 50 bar hydrogen pressure, hydrogenated to constant pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation. 856 parts of N- (3'-p-tertiary-butylphenyl-2'-methyl-propyl) -cis-2,6-dimethylmorpholine, bp 24 mbar = 206 ° C., are obtained. This corresponds to a yield of 94% of theory. Th. (Based on 3-p-tert-butylphenyl-2-methyl-prop-2-enal).

Beispiel 15Example 15

Ein Rührautoklav von 1000 Raumteilen Inhalt wird mit einer Mischung aus 153 Teilen 3-p-Terti- ärbutylphenyl-2-methyl-propanal, 75 Teilen Hexamethylenimin, 230 Teilen Methanol und 20 Teilen Katalysator, der aus 0,5% Pd, 5% Pr203, 1% Mn auf Al2O3 besteht, gefüllt. Nun wird bei 90°C und 50 bar Wasserstoffdruck bis zur Druckkonstanz hydriert. Danach lässt man den Autoklaven abkühlen, filtriert den Katalysator ab und reinigt das Filtrat destillativ. Hierbei werden 207 Teile N-[3-(p-Tertiärbutylphenyl)-2'-methyl-propyl]-hexamethylenimin, Kpo,26 mbar = 130°C, erhalten. Die Ausbeute beträgt 96% d. Th. (bez. auf 3-p-Tertiärbutyl-phenyl-2-methyl-propanal).A stirred autoclave of 1000 parts by volume is mixed with a mixture of 153 parts of 3-p-tert-butylphenyl-2-methyl-propanal, 75 parts of hexamethyleneimine, 230 parts of methanol and 20 parts of catalyst, which consists of 0.5% Pd, 5% Pr 2 0 3 , 1% Mn on Al 2 O 3 , filled. Now the mixture is hydrogenated to constant pressure at 90 ° C. and 50 bar hydrogen pressure. The autoclave is then allowed to cool, the catalyst is filtered off and the filtrate is purified by distillation. 207 parts of N- [3- (p-tertiary-butylphenyl) -2'-methyl-propyl] -hexamethyleneimine, Kp o , 26 mbar = 130 ° C., are obtained. The yield is 96% of theory. Th. (Based on 3-p-tertiary-butyl-phenyl-2-methyl-propanal).

Beispiel 16Example 16

Man verfährt analog Beispiel 14, verwendet aber als Carbonylkomponente 3-Phenyl-2-methyl-prop-2-enal. Hierbei fällt als Endprodukt N-(3'-Phenyl-2'-methylpropyl)-cis-2,6-dimethylmorpholin an,Kp0,05 mbar = 95°C. Die Ausbeute beträgt 93% d. Th.The procedure is analogous to Example 14, but 3-phenyl-2-me is used as the carbonyl component thyl-prop-2-enal. The end product obtained is N- (3'-phenyl-2'-methylpropyl) -cis-2,6-dimethylmorpholine, bp 0.05 mbar = 95 ° C. The yield is 93% of theory. Th.

Beispiel 17Example 17

Man verfährt analog Beispiel 15, verwendet aber als Aminkomponente 3,5-Dimethylpiperidin. Hierbei fällt als Endprodukt N-[3'-(p-Tertiärbutyi- phenyl)-2'-methylpropyl]-3,5-dimethylpiperidin an, Kp0.4 mbar = 135°C.The procedure is analogous to Example 15, but 3,5-dimethylpiperidine is used as the amine component. The end product obtained is N- [3 '- (p-tertiarybutylphenyl) -2'-methylpropyl] -3,5-dimethylpiperidine, bp 0.4 mbar = 135 ° C.

Beispiel 18-VergleichsbeispielExample 18 Comparative Example

Mit einem Katalysator der Zusammensetzung von 0,36 Gew.-% Pd, 4,8 Gew.-% Ag und 1,05 Gew.-% Mn auf Si02 wird völlig analog Beispiel 14 mit denselben Einsatzstoffen und unter denselben Reaktionsbedingungen gearbeitet. Das hierbei erhaltene Reaktionsprodukt hat nach gaschromatographischer Analyse folgende Zusammensetzung:

  • 46 Gew.-% N-(3'-p-Tertiärbutylphenyl-2'-methylpropyl)-cis-2,6-dimethylmorpholin, 25 Gew.-% N-(3'-p-Tertiärbutylphenyl-2'-methyl-prop-2'-enyl)-cis-2,6-dimethylmorpholin, 18 Gew.-% 3-p-Tertiärbutylphenyl-2-methyl-propanol und 11 Gew.-% cis-2,6-Dimethylmorpholin.
A catalyst having the composition of 0.36% by weight of Pd, 4.8% by weight of Ag and 1.05% by weight of Mn on SiO 2 is used, completely analogously to Example 14, with the same starting materials and under the same reaction conditions. The reaction product obtained in this way has the following composition according to gas chromatographic analysis:
  • 46% by weight of N- (3'-p-tertiary-butylphenyl-2'-methylpropyl) -cis-2,6-dimethylmorpholine, 25% by weight of N- (3'-p-tertiary-butylphenyl-2'-methyl-prop -2'-enyl) -cis-2,6-dimethylmorpholine, 18% by weight 3-p-tertiary-butylphenyl-2-methyl-propanol and 11% by weight cis-2,6-dimethylmorpholine.

Claims (1)

  1. A process for the preparation of an aralkyl- amine of the formula I
    Figure imgb0016
    where R1 is hydrogen, an aliphatic radical of 1 to 10 carbon atoms, a cycloaliphatic radical of 5 to 7 carbon atoms or alkoxy of 1 to 6 carbon atoms,
    R2, R3 and R4 are hydrogen or alkyl of 1 to 4 carbon atoms,
    X1, X2, X3 and X4 are hydrogen or alkyl of 1 to 4 carbon atoms,
    A is
    Figure imgb0017
    X5, X6, X7, X8, X9 and X10 are hydrogen or alkyl of 1 to 4 carbon atoms, and
    nis1,2,3,or4
    by reacting a secondary amine of the formula II
    Figure imgb0018
    where X1, X2, X3, X4 and A have the above meanings, with a carbonyl compound of the formula III
    Figure imgb0019
    where R1, R2, R3 and R4 have the above meanings, and the bond shown in broken lines may be a double bond or a single bond, characterized in that the reaction is carried out in the presence of hydrogen and of a hydrogenation catalyst which comprises palladium, mixed with zinc, cadmium, manganese and/or a rare earth metal oxide, on an inert carrier.
EP80101856A 1979-04-11 1980-04-08 Process for the preparation of heterocyclic tertiary aralkyl amines Expired EP0017893B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80101856T ATE768T1 (en) 1979-04-11 1980-04-08 PROCESS FOR THE PREPARATION OF HETEROCYCLIC TERTIARY ARALKYLAMINES.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2914646 1979-04-11
DE19792914646 DE2914646A1 (en) 1979-04-11 1979-04-11 N-Phenyl:propyl-heterocyclic amine derivs. prepn. - from aldehyde and amine by reductive amination, used as plant protectants or intermediates
DE2939060 1979-09-27
DE19792939060 DE2939060A1 (en) 1979-09-27 1979-09-27 N-Phenyl:propyl-heterocyclic amine derivs. prepn. - from aldehyde and amine by reductive amination, used as plant protectants or intermediates

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EP0017893A1 EP0017893A1 (en) 1980-10-29
EP0017893B1 true EP0017893B1 (en) 1982-03-24

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EP (1) EP0017893B1 (en)
CA (1) CA1128938A (en)
DE (1) DE3060242D1 (en)
HU (1) HU183120B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3105446A1 (en) * 1981-02-14 1982-09-02 Basf Ag, 6700 Ludwigshafen METHOD FOR PRODUCING ARALIPHATIC ALDEHYDES AND / OR AMINES
DE3421810A1 (en) * 1984-06-12 1985-12-12 Basf Ag, 6700 Ludwigshafen PHENYLALKYLAMINE - BIOREGULATORS
DE3633520A1 (en) * 1986-10-02 1988-04-14 Huels Chemische Werke Ag METHOD FOR PRODUCING N-SUBSTITUTED MORPHOLIN AND PIPERIDINE DERIVATIVES
SE8705150D0 (en) * 1987-12-23 1987-12-23 Haessle Ab NOVEL ANTIARRHYTHMIC AGENTS
ES2254686T3 (en) * 2001-03-16 2006-06-16 Basf Aktiengesellschaft PROCEDURE FOR OBTAINING 2,6-DIALQUYLMORPHOLINS N-SUBSTITUTED.
EP1749826A1 (en) * 2005-07-28 2007-02-07 Galderma S.A. Process of producing bepromoline

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1194865B (en) * 1956-06-29 1965-06-16 Lab Pharmaceutica Dr C Janssen Process for the preparation of 1, 1-diphenyl-3-hexamethylene-iminopropane and its salts
US2976321A (en) * 1959-06-18 1961-03-21 Givaudan Corp Para-tertiary-butylhydrocinnamic aldehyde
AT311969B (en) * 1971-03-15 1973-12-10 Lilly Industries Ltd Process for the preparation of new heterocyclic aminophenylalkylamines and of their acid addition salts
DE2656747C2 (en) * 1976-12-15 1984-07-05 Basf Ag, 6700 Ludwigshafen Morpholine derivatives
DE2727482A1 (en) * 1977-06-18 1979-01-11 Basf Ag DERIVATIVES OF CYCLIC AMINES

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US4283534A (en) 1981-08-11
EP0017893A1 (en) 1980-10-29
HU183120B (en) 1984-04-28
CA1128938A (en) 1982-08-03

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